Copolymers made of alkylene oxides and glycidyl ethers and use thereof as polymerizable emulsifiers

ABSTRACT

Disclosed are copolymers made of alkylene oxides and glycidyl ethers according to formula (I) 
     
       
         
         
             
             
         
       
     
     in which R 1  is hydrogen or a C 1 -C 4 -alkyl radical, R 2  and R 4  are an alkyl or aryl radical having 1 to 30 carbon atoms, and R 3  is an alkyl or aryl radical having 1 to 50 carbon atoms, which may also contain heteroatoms. A is an alkylene unit having 2 to 6 carbon atoms. In formula (1), x is a number from 0 to 10, y is a number from 0 to 10, n is a number from 0 to 100, k is a number from 1 to 100, R 5  is an acid group or hydrogen, and m is a number from 1 to 500, with the proviso that (y+n) must be at least 1.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No.10/525,151, filed Feb. 18, 2005, the disclosure of which is herebyincorporated herein by reference.

The present invention relates to copolymers made of alkylene oxides andglycidyl ethers which can be used as free-radically polymerizableemulsifiers for emulsion polymerization.

The emulsifiers used for emulsion polymerization according to the priorart are in most cases anionic and nonionic emulsifiers.

Customary anionic emulsifiers are sodium, potassium and ammonium saltsof fatty acids, sodium alkylbenzenesulfonates, sodium alkylsulfonates,sodium olefinsulfonates, sodium polynaphthalenesulfonates, sodiumdialkyl diphenyl ether disulfonates, sodium, potassium and ammoniumalkyl sulfates, sodium, potassium and ammonium alkyl polyethylene glycolether sulfates, sodium, potassium and ammonium alkylphenol polyethyleneglycol ether sulfates, sodium, potassium and ammonium mono- and dialkylsulfosuccinates and monoalkyl polyoxyethyl sulfosuccinates, and alsoalkyl polyethylene glycol ether phosphoric mono-, di- and triesters andmixtures thereof and alkylphenol polyethylene glycol ether phosphoricmono-, di- and triesters and mixtures thereof, and the sodium, potassiumand ammonium salts thereof.

The nonionic emulsifiers customarily used are alkylphenol polyethyleneglycol ethers, alkyl polyethylene glycol ethers, fatty acid polyethyleneglycol ethers, ethylene/propylene glycol block polymers and sorbitanester polyethylene glycol ethers.

Emulsion polymerizations are carried out using anionic and nonionicemulsifiers usually with the total batch as the initial charge or in afeed process in which only a small part of the monomers to bepolymerized is initially introduced into the polymerization vessel andthe larger part (50 to 100% by weight) is added as the polymerizationprogresses. The anionic or nonionic emulsifiers are used as desiredduring the emulsion polymerization in the feed or in the reactor initialcharge, or are added subsequently to the prepared polymer dispersion forstabilization.

In this connection, the emulsifiers used according to the prior art arebonded to the surface of the polymer particles via physical forces.

EP-A-0 244 841 discloses surface-active components with a polymerizableunit which can be chemically incorporated into the polymer particle byfree-radical polymerization reactions. These components are reactionproducts of glycerol monoallyl ethers with a hydrophobic and ahydrophilic substitution radical on the OH groups of the glycerolmonoallyl ether.

J. Polym. Sci., 30 (1992) 2619-2629 and J. Polym. Sci., 31 (1993)1403-1415 disclose the use of sodium dodecylallyl sulfosuccinate ascopolymerizable emulsifier in the emulsion polymerization of vinylacetate.

EP-A-0 501 666 discloses aqueous polymer dispersions which have beenprepared by emulsion polymerization using free-radically polymerizableemulsifiers.

EP-A-0 472 837 discloses (1-propenyl)alkylphenol ethoxylates asemulsifiers for emulsion polymerization. EP-A-0 464 454 discloses thesulfuric esters of the (1-propenyl)alkylphenol ethoxylates asemulsifiers for emulsion polymerization.

JP-A-11-71340 discloses allyl- and vinylpolyoxyalkylenylalkylsulfonatesas emulsifiers for emulsion polymerization, as dispersants forsuspension polymerization and as polymer modifiers.

JP-A-2002-080506 discloses polymerizable emulsifiers with3-methyl-3-buten-1-yl radicals which may contain glycidyl units.

JP-A-2002-097212 discloses polymerizable emulsifiers with allyl groupsbonded directly to the glycidyl radical.

It was therefore an object of the present invention to find novelemulsifiers for emulsion polymerization. These emulsifiers shouldcopolymerize with the monomers used and thus be bonded chemically in thepolymer particles, and produce polymers with advantageous properties,such as improved stability of the polymer dispersions which can beprepared therewith and a more homogeneous particle size distribution.

It has now been found that using copolymers made of alkylene oxides andglycidyl ethers which carry a double bond as reactive group, and alsopartial esters, sulfonic acids and carboxylic acids thereof asemulsifiers in the emulsion polymerization, it is possible to preparestable and low-coagulum polymer dispersions.

The invention thus provides copolymers made of alkylene oxides andglycidyl ethers according to formula (I)

in which

R¹ is hydrogen or a C₁-C₄-alkyl radical,

R² and R⁴ are an alkyl or aryl radical having 1 to 30 carbon atoms,

R³ is an alkyl or aryl radical having 1 to 50 carbon atoms which mayalso contain heteroatoms,

A is an alkylene unit having 2 to 6 carbon atoms,

x is a number from 0 to 10,

y is a number from 0 to 10,

n is a number from 0 to 100,

k is a number from 1 to 100,

R⁵ is an acid group or hydrogen, and

m is a number from 1 to 500,

with the proviso that (y+n) must be at least 1.

The invention further provides those compounds of the formula 1 in whichx, y and n are simultaneously zero, and in which R¹, R², R³, R⁴, A, R⁵and have the meaning given above.

The emulsifiers according to the invention are notable for the fact thatthe reactive double bond is bonded to the glycerol unit in the moleculevia the alkoxy units with the indices y and n as flexible “spacer”. The“spacer” can additionally contribute to the stabilization of the polymerdispersion.

In a preferred embodiment of the invention, the alcohols of the formula1 are those alkoxylates whose alkoxy groups are arranged in blocks.

x in a preferred embodiment is 0 or 1.

y in a preferred embodiment is 0 or 1.

n in a preferred embodiment is a number from 2 to 50, in particular 3 to30.

k in a preferred embodiment is a number from 1 to 50, in particular 2 to30.

m in a preferred embodiment is a number from 2 to 100, in particular 3to 50.

R² and R⁴ in a preferred embodiment are a hydrogen atom or a methylgroup.

The sum (y+n) is preferably at least 2, in particular at least 3 andspecifically at least 4.

Examples of inorganic acids which are suitable for the formation of thepartial esters according to the invention and from which the acid groupR⁵ can be derived are sulfuric acid and phosphoric acid. If phosphoricacid is used, then the partial esters according to the invention mayeither be monoesters or diesters of phosphoric acid.

In a preferred embodiment, the organic or inorganic acids used for theesterification of the alcohols according to formula 1 are dibasic ortribasic.

In a preferred embodiment, the organic acids are dibasic, tribasic orpolybasic carboxylic acids, i.e. compounds which contain 2, 3 or morecarboxyl groups and which moreover can also have at least one sulfur- orphosphorus-containing functional group. Particular preference is givento sulfur-containing functional groups, specifically sulfonate groups.

The particularly preferred sulfonic acids/sulfonates may be aliphatic oraromatic compounds. Preferred sulfonic acids/sulfonates contain 2 or 3carboxyl groups and, including the carboxyl groups, 3 to 6 carbon atoms.A particularly preferred sulfonic acid is sulfosuccinic acid.

In a preferred embodiment, the sulfonic and carboxylic acids arearomatic or aliphatic compounds which carry one or more acid functions.

Particularly preferred partial esters and acid derivatives thuscorrespond to the formulae (2) to (7)

in which R¹, R², R³, R⁴, x, y, m, k and n have the meanings given above,M is an alkali metal ion, an ammonium ion or is H⁺, and B is analiphatic or aromatic group having 1 to 50 carbon atoms which may alsocontain heteroatoms.

The partial esters according to the invention can be prepared byreacting the alcohols of the formula 1 with suitable acids. However, itis to be ensured that the acids do not have an oxidizing effect sinceotherwise oxidation of the double bond is possible. For this reason, thepreparation of sulfate partial esters is preferably carried out withamidosulfonic acid instead of with sulfuric acid. The resulting ammoniumsalts can be converted to the corresponding alkali metal salts byreaction with alkali metal hydroxides. For the preparation of phosphoricpartial esters, it is possible to use phosphoric acid. Organic acids arepreferably reacted in the form of their anhydrides with the alcohols ofthe formula 1. The insertion of functional groups preferably takes placefollowing the preparation of the partial ester of the nonfunctionalizedacid. Thus, the preparation of the sulfosuccinic esters according toformula 5 can be carried out by preparing the corresponding maleicesters and subsequent sulfonation, e.g. with pyrosulfites.

The sulfonic acids, carboxylic acids and phosphonic acids are preparedby reacting the alcohols of the formula 1 with the correspondingalcohols, halides or cyclic esters of sulfonic or carboxylic acids.

The invention further provides the use of the copolymers according tothe invention as polymerizable emulsifiers in emulsion polymerization.

The invention further provides a process for emulsion polymerization inwhich the copolymers according to the invention are added to thereaction mixture.

In this use, the copolymers according to the invention are polymerizedwith further monomers from which a polymer dispersion is to be prepared.Unsaturated monomers are suitable for the preparation of polymerdispersions. Preferred olefinically unsaturated monomers are, forexample,

vinyl monomers, such as carboxylic esters of vinyl alcohol, for examplevinyl acetate, vinyl propionate, vinyl ethers of isononanoic acid or ofisodecanoic acid,

aryl-substituted olefins, such as styrene and stilbene

olefinically unsaturated carboxylic esters, such as methyl acrylate,ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate,pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, hydroxyethylacrylate, and the corresponding methacrylic esters,

olefinically unsaturated dicarboxylic esters, such as dimethyl maleate,diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate,dihexyl maleate, di-2-ethylhexyl maleate,

olefinically unsaturated carboxylic acids and dicarboxylic acids, suchas acrylic acid, methacrylic acid, itaconic acid, maleic acid andfumaric acid and their sodium, potassium and ammonium salts,

olefinically unsaturated sulfonic acids and phosphonic acids and theiralkali metal and ammonium salts, such asacrylamidomethyl-propanesulfonic acid and its alkali metal and ammonium,alkyl-ammonium and hydroxyalkylammonium salts, allylsulfonic acid andits alkali metal and ammonium salts, acryloyloxyethylphosphonic acid andits ammonium and alkali metal salts, and also the correspondingmethacrylic acid derivatives,

olefinically unsaturated amines, ammonium salts, nitriles and amides,such as dimethylaminoethyl acrylate, acryloyloxyethyl-trimethylammoniumhalides, acrylonitrile, N-methylacrylamide, N-ethylacrylamide,N-propylacrylamide, N-methylolacrylamide, and the correspondingmethacrylic acid derivatives and vinylmethylacetamide.

In a preferred embodiment, the abovementioned monomers are polymerizedwith further comonomers, preferably olefins or halogenated olefins with2 to 8 carbon atoms, such as, for example, ethylene, propene, butenes,pentenes, 1,3-butadiene, chloroprene, vinyl chloride, vinylidenechloride, vinylidene fluoride and tetrafluoroethylene.

The invention consequently provides a process for the preparation ofpolymer dispersions by polymerizing the copolymers according to theinvention with olefinically unsaturated monomers in the aqueous phase,and also the aqueous polymer dispersion preparable in this way.

To prepare the polymer dispersions, the water-immiscible monomers aregenerally finely distributed in the aqueous phase in the form ofmicelles using the copolymers according to the invention, and thefree-radical polymerization reaction is started by initiators such as,for example, ammonium peroxodisulfate, sodium peroxodisulfate andpotassium peroxodisulfates.

Further auxiliaries and additives for the use with the copolymersaccording to the invention may be protective colloids, such ascarboxymethylcellulose, hydroxyethylcellulose,methylhydroxypropylcellulose, and also partially and completelysaponified polyvinyl alcohol.

A review of common processes, surfactants and further auxiliaries ofemulsion polymerization is given by Peter A. Lovell and Mohamed S.El-Aasser, in “Emulsion Polymerization and Emulsion Polymers”, publishedby John Wiley and Sons, 1997.

The copolymers according to the invention are initially introduced intothe reaction vessel prior to the start of the polymerization reaction oradded to the reaction vessel during the polymerization reaction.

In general, the copolymers according to the invention are used asemulsifiers in amounts of from 0.1 to 50% by weight, preferably 0.2 to10% by weight, in particular 0.4 to 4% by weight, based on the weight ofthe water-insoluble or sparingly water-soluble olefinically unsaturatedmonomers used for the preparation of the polymer dispersion.

The copolymers according to the invention can either be used on theirown or else in combination with other already known anionic and nonionicemulsifiers of the prior art, as described at the beginning. The amountof anionic and nonionic emulsifiers of the prior art is then preferably0.001 to 5% by weight, in particular 0.01 to 1% by weight andparticularly preferably 0.02 to 0.4% by weight, based on the weight ofthe water-insoluble or sparingly water-soluble olefinically unsaturatedmonomers.

The polymer dispersions prepared using the copolymers according to theinvention exhibit low coagulum formation during and afterpolymerization, and an improvement in the shear stability, thermalstability and storage stability, the freeze/thaw stability and theelectrolyte stability toward divalent and trivalent cations such ascalcium, barium and aluminum. In addition, an improvement in the filmproperties of the polymer films prepared from the polymer dispersions isobserved. The polymer dispersions prepared using the copolymersaccording to the invention form films with low water absorption, lowblushing upon contact with water, a small contact angle toward water andgood wet and dry rubbing fastnesses. The polymer dispersions preparedwith the copolymers according to the invention exhibit very smallparticle sizes with very narrow particle size distributions, dependingon the monomer composition and the amount used.

EXAMPLES

Preparation of copolymers of alkylene oxides and glycidyl ethers withallyl units (formula 1).

Example 1 Ethylene Oxide-Phenyl Glycidyl Ether Copolymer Initiated withAllyl Alcohol Mw ca. 1300 g/mol

1 mol of allyl alcohol was partially reacted with 0.1 mol of sodiummethanolate in an inert solvent (monoglyme) in a laboratory autoclave togive the alkoxide. Methanol was distilled off. 5 mol of ethylene oxidewere then added and the mixture was polymerized under pressure for 5hours at about 140° C. 1.1 mol of phenyl glycidyl ether were addeddropwise to this reaction product and stirred for 15 hours at 90° C. andthen a further 20 mol of ethylene oxide were added at 140° C. After theethylene oxide had completely reacted, the product was analyzed usingNMR spectroscopy and OH number determination.

The OH number was 44.5 mg of KOH/g

The NMR spectrum corresponded to the following structures:

Example 2 Propylene Oxide-Ethylene Oxide-Phenyl Glycidyl Ether CopolymerInitiated with Allyl Alcohol Mw 1000 g/mol

1 mol of allyl alcohol was partially reacted with 0.1 mol of potassiummethanolate in an inert solvent (monoglyme) in a laboratory autoclave togive the alkoxide. Methanol was distilled off. 4 mol of propylene oxidewere then added and the mixture was polymerized under pressure for 5hours at about 140° C. 1.1 mol of phenyl glycidyl ether were addeddropwise to this reaction product and stirred again for 15 hours at 90°C. 12 mol of ethylene oxide were then added at 140° C. After theethylene oxide had completely reacted, the product was analyzed usingNMR spectroscopy and OH number determination.

The OH number was 57.9 mg of KOH/g

The NMR spectrum corresponded to the following structures:

Example 3 Propylene Oxide-Ethylene Oxide-Phenyl Glycidyl Ether CopolymerInitiated with Allyl Alcohol Mw 1500 g/mol

1 mol of allyl alcohol was partially reacted with 0.1 mol of potassiummethanolate in an inert solvent (monoglyme) in a laboratory autoclave togive the alkoxide. Methanol was distilled off. 4 mol of propylene oxidewere then added and polymerized under pressure for 5 hours at about 140°C. 1.1 mol of phenyl glycidyl ether were added dropwise to this reactionproduct, and stirred again for 15 hours at 90° C. 25 mol of ethyleneoxide were then added at 140° C. After the ethylene oxide had completelyreacted, the product was analyzed using NMR spectroscopy and OH numberdetermination.

The OH number was 40.5 mg of KOH/g

The NMR spectrum corresponded to the following structures:

Example 4 Butylene Oxide-Ethylene Oxide-(2-Ethylhexyl) Glycidyl EtherCopolymer Initiated with Allyl Alcohol Mw 1700 g/mol

1 mol of allyl alcohol was partially reacted with 0.1 mol of potassiummethanolate in an inert solvent (monoglyme) in a laboratory autoclave togive the alkoxide. Methanol was distilled off. 4 mol of butylene oxidewere then added and polymerized under pressure for 5 hours at about 140°C. 1.1 mol of (2-ethylhexyl) glycidyl ether were added dropwise to thisreaction product, and stirred again for 15 hours at 90° C. 26 mol ofethylene oxide were then added at 140° C. After the ethylene oxide hadcompletely reacted, the product was analyzed using NMR spectroscopy andOH number determination.

The OH number was 32.9 mg of KOH/g

The NMR spectrum corresponded to the following structures:

Example 5 Propylene Oxide-Ethylene Oxide-Phenyl Glycidyl Ether CopolymerInitiated with Hydroxybutyl Vinyl Ether, Mw 2600 g/mol

1 mol of hydroxybutyl vinyl ether was partially reacted with 0.1 mol ofpotassium methanolate in an inert solvent (monoglyme) in a laboratoryautoclave to give the alkoxide. Methanol was distilled off. 10 mol ofpropylene oxide were then added and polymerized under pressure for 5hours at about 140° C. 1.1 mol of phenyl glycidyl ether were addeddropwise to this reaction product, and stirred again for 15 hours at 90°C. 40 mol of ethylene oxide were then added at 140° C. After theethylene oxide had completely reacted, the product was analyzed usingNMR spectroscopy and OH number determination.

The OH number was 20.5 mg of KOH/g

The NMR spectrum corresponded to the following structures:

Preparation of Partial esters

Example 6

197 g of the alcohol from example 2 were admixed, under nitrogen, with19.4 g of amidosulfonic acid and 0.5 g of 50% strength hypophosphorousacid. The mixture was heated, with vigorous stirring, at 80° C. for 5 hand at 100° C. for 1 h. When the reaction was complete, the mixture wasleft to cool and admixed with 1.8 g of 20% strength NaOH. 212 g (98%) ofthe sulfuric monoester were obtained.

Example 7

787 g of the alcohol from example 1 were admixed, under nitrogen, with60.7 g of amidosulfonic acid and 1.88 g of urea and stirred vigorouslyat 100° C. for 3 h. When the reaction was complete, the mixture was leftto cool and admixed with 2.5 g of 20% strength NaOH. 832 g (98%) of thesulfuric monoester were obtained.

Example 8

428 g of the sulfuric monoester ammonium salt prepared in example 7 wereheated to 60° C. At 200 mbar, 105 g of 18% strength NaOH were addeddropwise and then the mixture was after-reacted for a further 2 h at 50mbar, during which the introduced water was driven off together with theammonia. This gave 421 g (98%) of the sulfuric monoester sodium salt.

Example 9

1275 g of the alcohol from example 4 were admixed, under nitrogen, with72.8 g of amidosulfonic acid and 2.25 g of urea and stirred vigorouslyat 120° C. for 8 h. When the reaction was complete, the mixture was leftto cool and admixed with 3 g of 20% strength NaOH. 1336 g (99%) of thesulfuric monoester were obtained.

Example 10

634 g of the alcohol from example 1 were admixed, under nitrogen, with48 g of amidosulfonic acid and 1.5 g of urea. With vigorous stirring,the mixture is heated at 100° C. for 4 h. When the reaction wascomplete, the mixture was left to cool and 1 g of 18% strength NaOH wasadded. 677 g (99%) of the sulfuric monoester were obtained.

Example 11

1260 g of the alcohol from example 1 were added dropwise (undernitrogen) to 98 g of maleic anhydride at 70° C. The mixture was thenheated at 90° C. for 4 h and added to a mixture of 52 g of sodiumpyrosulfite, 40 g of NaOH and 960 g of distilled water and reacted for 5h at 80° C. 2410 g of sulfosuccinate solution with a content of 60% byweight were obtained.

Example 12

1275 g of the alcohol from example 4 were added dropwise, undernitrogen, to 74 g of maleic anhydride at 70° C. The mixture was thenheated at 90° C. for 8 h, during which the water which formed wasdistilled off. The resulting product was added to a mixture of 39 g ofsodium pyrosulfite, 30 g of NaOH and 1430 g of distilled water andheated at 80° C. for 5 h. 2830 g of sulfosuccinate solution with acontent of 50% by weight were obtained.

Example 13

606 g of the alcohol from example 2 were admixed with 71 g ofpoly-phosphoric acid at 70° C. and stirred for 2 h at 70° C. After afurther 3 h at 100° C., 24 g of water were added at 90° C. and themixture was stirred for a further 2 h. This gave 560 g of product, whichwas a mixture of 80% by weight of phosphoric monoester and 7% by weightof phosphoric diester, remainder water. The product contained nophosphoric triester.

Example 14

1260 g of the alcohol from example 1 were admixed with 113 g ofpoly-phosphoric acid at 70° C. and stirred for 2 h at 70° C. After afurther 2 h at 100° C., 30 g of water were added at 90° C. and themixture was stirred for a further 2 h. This gave 1400 g of product,which was a mixture of 82% by weight of phosphoric monoester and 8% byweight of phosphoric diester, remainder water. The product contained nophosphoric triester.

Examples of the Preparation of sulfonic acids Example 15

850 g of alcohol from example 4 were admixed, under nitrogen at 50® C.,with 81 g of 3-hydroxypropanesulfonic acid sodium salt and 20 g of NaOHprills and stirred for 3 h. The mixture was then stirred for a further 2h at 70° C. The lower phase was discarded and the upper phase wasneutralized with 5 g of acetic acid. This gave 855 g (96%) of thedesired sulfonic acid ether.

Example 16

728 g of alcohol from example 2 were admixed, under nitrogen at 50° C.,with 174 g of 4-hydroxybenzenesulfonic acid sodium salt dihydrate and 30g of NaOH prills and stirred for 1 h. The mixture was then stirred for afurther 2 h at 70° C. The lower phase was discarded and the upper phasewas neutralized with 7 g of acetic acid. This gave 810 g (94%) of thedesired sulfonic acid ether.

Example 17

650 g of the alcohol from example 5 were admixed with 11 g of sodiumhydroxide prills and dried under reduced pressure for 2 hours at 100° C.0.25 mol (34 g) of butanesultone were then added dropwise under nitrogenat 90° C. and stirred for 6 hours. The α-vinyloxy-Ω-sulfonate-ethyleneoxide-propylene oxide-phenyl glycidyl block copolymer was obtained,according to NMR analysis, with 70% yield. The NMR spectrum correspondedto the following structures:

Examples for the Preparation of carboxylic acids Example 18

630 g of alcohol from example 1 were admixed, under nitrogen at 50° C.,with 59 g of chloroacetic acid sodium salt and 20 g of NaOH prills andstirred for 3 h. The mixture was then stirred for a further 4 h at 70°C. The lower phase was discarded and the upper phase was neutralizedwith 6 g of acetic acid. This gave 650 g (97%) of the desired carboxylicacid ether.

Example 19

1275 g of alcohol from example 4 were admixed, under nitrogen at 50° C.,with 120 g of 4-hydroxybenzoic acid sodium salt and 30 g of NaOH prillsand stirred for 1 h. The mixture was then stirred for a further 2 h at80° C. The lower phase was discarded and the upper phase was neutralizedwith 10 g of acetic acid. This gave 1320 g (96%) of the desiredcarboxylic acid ether.

Preparation of polymer Dispersions

Example 20

Styrene/acrylate Dispersion

1020 g of a monomer emulsion consisting of 331.8 g of demineralizedwater, 4.8 g of ®Emulsogen EPA 073 (sodium alkyl polyethylene glycolether sulfate, Clariant GmbH), 13.2 g of the sulfuric monoesteraccording to the invention from example 10, 3.6 g of sodiumhydrogencarbonate, 216 g of styrene, 300 g of n-butyl acrylate, 144 g ofmethyl acrylate and 6.6 g of methacrylic acid, and an initiator solutionconsisting of 3.33 g of ammonium peroxodisulfate and 85.5 ml ofdemineralized water were prepared.

204.54 g of demineralized water were initially introduced into a 2 literreaction vessel, and 6.6 g of the sulfuric monoester according to theinvention from example 10 were added. Under a nitrogen atmosphere andwith stirring using an anchor stirrer, the emulsifier solution washeated to 80° C. in the reaction vessel. 22.2 ml of initiator solutionand 25.5 ml of the monomer emulsion were then added. The free-radicalpolyaddition reaction starts. The reaction mixture was cooled and keptconstant at 79-81° C. over the water bath. The remaining 994.5 g of themonomer emulsion and 66.6 g of the initiator solution were added over aperiod of 3 hours. The reaction mixture was then kept for a further hourat 80° C. over the water bath and then cooled to room temperature. ThepH of the prepared polymer dispersion was adjusted to pH 7-8 using 12.5%strength ammonia solution.

The resulting polymer dispersion has a solids content of 52% and acoagulum of <0.006% through a 100 μm sieve and of <0.006% through a 40μm sieve, based on the dispersion. The average particle size (Z_(AVE)),measured by means of dynamic light scattering, is 144 nm with apolydispersity of 0.035.

Example 21

Styrene/acrylate Dispersion

1020 g of a monomer emulsion consisting of 336.6 g of demineralizedwater, 13.2 g of the sulfuric monoester according to the invention as inexample 10, 3.6 g of sodium hydrogencarbonate, 216 g of styrene, 300 gof n-butyl acrylate, 144 g of methyl acrylate and 6.6 g of methacrylicacid, and an initiator solution consisting of 3.33 g of ammoniumperoxodisulfate and 85.5 ml of demineralized water were prepared.

204.54 g of demineralized water were initially introduced into a 2 literreaction vessel and 6.6 g of the sulfuric monoester according to theinvention from example 10 were added. Under a nitrogen atmosphere andwith stirring using an anchor stirrer, the emulsifier solution in thereaction vessel was heated to 80° C. 22.2 ml of initiator solution and25.5 ml of the monomer emulsion were then added. The free-radicalpolyaddition reaction starts. The reaction mixture was cooled and keptconstant at 79-81° C. over the water bath. The remaining 994.5 g of themonomer emulsion and 66.6 g of the initiator solution were added over aperiod of 3 hours. Then, over the water bath, the reaction mixture waskept at 80° C. for a further hour and then cooled to room temperature.The pH of the prepared polymer dispersion was adjusted to pH 7-8 with12.5% strength ammonia solution.

The resulting polymer dispersion had a solids content of 52% and acoagulum of <0.008% through a 100 μm sieve and of <0.008% through a 40μm sieve, based on the dispersion. The average particle size (Z_(AVE)),measured by means of dynamic light scattering, is 132 nm with apolydispersity of 0.028.

Example 22

Straight acrylate Dispersion

1800 g of a monomer emulsion consisting of 397.2 g of demineralizedwater, 9.6 g of Emulsogen EPA 073 (sodium alkyl polyethylene glycolether sulfate), 27.0 g of the sulfuric monoester according to theinvention as in example 10, 2.2 g of dodecyl mercaptan, 150 g of methylmethacrylate, 350 g of 2-ethylhexyl acrylate, 850 g of n-butyl acrylateand 14 g of methacrylic acid, and 57 g of an initiator solutionconsisting of 7.1 g of ammonium peroxodisulfate and 49.9 g ofdemineralized water were prepared.

263 g of demineralized water were initially introduced into a 3 literreaction vessel and heated to 80° C. under a nitrogen atmosphere over awater bath. 17 g of the initiator solution were then added, and thecontinuous addition of the 1800 g of monomer emulsion and the remaining40 g of initiator solution was immediately started. The metered additionof the two components was carried out with continuous stirring using ananchor stirrer and under a nitrogen atmosphere over a period of 3 hours.The reaction mixture was then heated at 80° C. for a further hour andthen cooled to room temperature. The pH of the prepared polymerdispersion was adjusted to pH 7-8 using 12.5% strength ammonia solution.

The resulting polymer dispersion had a solids content of 65% and acoagulum of <0.1% through a 100 μm sieve and of <0.2% through a 40 μmsieve, based on the dispersion.

Example 23

Styrene/acrylate Dispersion

1020 g of a monomer emulsion consisting of 331.8 g of demineralizedwater, 6.6 g of the alcohol according to the invention from example 1,6.6 g of ®Emulsogen EPA 073 (sodium alkylpolyethylene glycol ethersulfate, Clariant GmbH), 3.6 g of sodium hydrogencarbonate, 216 g ofstyrene, 300 g of n-butyl acrylate, 144 g of methyl acrylate and 6.6 gof methacrylic acid, and an initiator solution consisting of 3.33 g ofammonium peroxodisulfate and 85.5 ml of demineralized water wereprepared.

204.54 g of demineralized water were initially introduced into a 2 literreaction vessel and 6.6 g of the sulfuric monoester according to theinvention were added. Under a nitrogen atmosphere and with stirringusing an anchor stirrer, the emulsifier solution was heated to 80° C. inthe reaction vessel. 22.2 ml of initiator solution and 25.5 ml of themonomer emulsion were then added. The free-radical polyaddition reactionstarts.

The reaction mixture was cooled and kept constant at 79-81° C. over thewater bath. The remaining 994.5 g of the monomer emulsion and 66.6 g ofthe initiator solution were added over a period of 3 hours. Then, overthe water bath, the reaction mixture was kept at 80° C. for a furtherhour and then cooled to room temperature. The pH of the prepared polymerdispersion was adjusted to pH 7-8 with 12.5% strength ammonia solution.

The resulting polymer dispersion had a solids content of 52% and acoagulum of <0.1% through a 100 μm sieve and of <0.15% through a 40 μmsieve, based on the dispersion.

Example 24

Styrene/acrylate Dispersion

1020 g of a monomer emulsion consisting of 331.8 g of demineralizedwater, 6.6 g of the alcohol according to the invention from example 1,6.6 g of the alcohol according to the invention from example 10, 3.6 gof sodium hydrogencarbonate, 216 g of styrene, 300 g of n-butylacrylate, 144 g of methyl acrylate and 6.6 g of methacrylic acid, and aninitiator solution consisting of 3.33 g of ammonium peroxodisulfate and85.5 ml of demineralized water were prepared.

204.54 g of demineralized water were initially introduced into a 2 literreaction vessel and 6.6 g of the sulfuric monoester according to theinvention were added. Under a nitrogen atmosphere and with stirringusing an anchor stirrer, the emulsifier solution was heated to 80° C. inthe reaction vessel. 22.2 ml of initiator solution and 25.5 ml of themonomer emulsion were then added. The free-radical polyaddition reactionstarts. The reaction mixture was cooled and kept constant at 79-81° C.over the water bath. The remaining 994.5 g of the monomer emulsion and66.6 g of the initiator solution were added over a period of 3 hours.Then, over the water bath, the reaction mixture was kept at 80° C. for afurther hour and then cooled to room temperature. The pH of theresulting polymer dispersion was adjusted to pH 7-8 with 12.5% strengthammonia solution.

The resulting polymer dispersion had a solids content of 52% and acoagulum of <0.01% through a 100 μm sieve and of <0.05% through a 40 μmsieve, based on the dispersion.

Vinyl acetate/acrylate Dispersion

960 g of a monomer emulsion consisting of 271.44 g of demineralizedwater, 11.76 g of ®Emulsogen EPA 073 (sodium alkyl polyethylene glycolether sulfate, Clariant GmbH), 6.6 g of the sulfuric monoester accordingto the invention from example 10, 3.6 g of sodium hydrogencarbonate, 528g of vinyl acetate, 128 g of n-butyl acrylate and 6.6 g of methacrylicacid, and an initiator solution consisting of 2.33 g of ammoniumperoxodisulfate and 59.87 ml of demineralized water were prepared.

293.09 g of demineralized water were initially introduced into a 2 literreaction vessel and 4.69 g of ®Emulsogen EPA 073 (sodium alkylpolyethylene glycol ether sulfate, Clariant GmbH) and 0.12 g of sodiumdisulfite were added. Under a nitrogen atmosphere and with stirringusing an anchor stirrer, the emulsifier solution was heated to 80° C. inthe reaction vessel. 18.66 ml of initiator solution and 24 ml of themonomer emulsion were then added. The free-radical polyaddition reactionstarts. The reaction mixture is cooled and kept constant at 79-81° C.over the water bath. The remaining 936 g of the monomer emulsion and43.54 g of the initiator solution were added over a period of 3.5 hours.Then, over the water bath, the reaction mixture was kept at 80° C. for afurther hour and then cooled to room temperature.

The resulting polymer dispersion has a solids content of 51% and acoagulum of <0.007% through a 100 μm sieve and of <0.013% through a 40μm sieve, based on the dispersion. The average particle size (Z_(AVE)),measured by means of dynamic light scattering, is 149 nm with apolydispersity of 0.026.

Vinyl acetate/acrylate Dispersion

960 g of a monomer emulsion consisting of 279.9 g of demineralizedwater, 13.2 g of the sulfuric monoester according to the invention fromexample 10, 3.6 g of sodium hydrogencarbonate, 528 g of vinyl acetate,128 g of n-butyl acrylate and 6.6 g of methacrylic acid, and aninitiator solution consisting of 2.33 g of ammonium peroxodisulfate and59.87 ml of demineralized water were prepared.

296.46 g of demineralized water were initially introduced into a 2 literreaction vessel, and 1.32 g of the sulfuric monoester according to theinvention from example 10 and 0.12 g of sodium disulfite were added.Under a nitrogen atmosphere and with stirring using an anchor stirrer,the emulsifier solution was heated to 80° C. in the reaction vessel.18.66 ml of initiator solution and 24 ml of the monomer emulsion werethen added. The free-radical polyaddition reaction starts. The reactionmixture was cooled and kept constant at 79-81° C. over the water bath.The remaining 936 g of the monomer emulsion and 43.54 g of the initiatorsolution were added over a period of 3.5 hours. Then, over the waterbath, the reaction mixture was kept at 80° C. for a further hour andthen cooled to room temperature.

The resulting polymer dispersion has a solids content of 51% and acoagulum of <0.005% through a 100 μm sieve and of <0.007% through a 40μm sieve, based on the dispersion. The average particle size (Z_(AVE)),measured by means of dynamic light scattering, is 240 nm with a verynarrow polydispersity of 0.009.

1. A process for producing a block polymer of formula (1), said processcomprising reacting an alkylene oxide and a glycidal ether in anemulsion polymerization reaction

in which R¹ is hydrogen or a C¹-C⁴-alkyl radical, R² and R⁴ are an alkylor aryl radical having 1 to 30 carbon atoms, R³ is an alkyl or arylradical having 1 to 50 carbon atoms which may also contain heteroatoms,A is an alkylene unit having 2 to 6 carbon atoms, x is a number from 0to 10, y is a number from 0 to 10, n is a number from 0 to 100, k is anumber from 1 to 100, R⁵ is an acid group or hydrogen, and m is a numberfrom 1 to 500, with the proviso that (y+n) must be at least
 1. 2. Theprocess of claim 1, in which R⁵ is the radical of a dibasic acid ortribasic acid.
 3. A process for the preparation of polymer dispersions,said process comprising reacting an alkylene oxide and a glycidal etherin an emulsion polymerization reaction

in which R¹ is hydrogen or a C₁-C₄-alkyl radical, R² and R⁴ are an alkylor aryl radical having 1 to 30 carbon atoms, R³ is an alkyl or arylradical having 1 to 50 carbon atoms which may also contain heteroatoms,A is an alkylene unit having 2 to 6 carbon atoms, x is a number from 0to 10, y is a number from 0 to 10, n is a number from 0 to 100, k is anumber from 1 to 100, R⁵ is an acid group or hydrogen, and m is a numberfrom 1 to 500, with the proviso that (y+n) must be at least 1, andwherein said polymerization reaction is carried out in the presence ofan olefinically unsaturated monomer in an aqueous phase.
 4. The processof claim 3 wherein the olefinically unsaturated comonomer is selectedfrom the group consisting of vinyl monomers, aryl-substituted olefins,olefinically unsaturated carboxylic esters, olefinically unsaturateddicarboxylic esters, olefinically unsaturated carboxylic acids anddicarboxylic acids, olefinically unsaturated sulfonic acids andphosphonic acids and their alkali metal and ammonium salts, olefinicallyunsaturated amines, ammonium salts, nitriles and amides.
 5. The processof claim 3 wherein the olefinically unsaturated monomer is polymerizedwith a further comonomer which is an olefin or a halogenated olefinhaving 2 to 8 carbon atoms.